JP6083490B2 - Method for producing inorganic fine particle dispersion and method for producing cured product for optical member - Google Patents
Method for producing inorganic fine particle dispersion and method for producing cured product for optical member Download PDFInfo
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- JP6083490B2 JP6083490B2 JP2016517005A JP2016517005A JP6083490B2 JP 6083490 B2 JP6083490 B2 JP 6083490B2 JP 2016517005 A JP2016517005 A JP 2016517005A JP 2016517005 A JP2016517005 A JP 2016517005A JP 6083490 B2 JP6083490 B2 JP 6083490B2
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- meth
- inorganic fine
- fine particle
- producing
- dispersion
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- 239000006185 dispersion Substances 0.000 title claims description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000010419 fine particle Substances 0.000 title claims description 18
- 230000003287 optical effect Effects 0.000 title claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 32
- 239000002270 dispersing agent Substances 0.000 claims description 26
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 21
- -1 acryloyloxy group Chemical group 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 239000002105 nanoparticle Substances 0.000 claims description 18
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000002612 dispersion medium Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
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- 238000006243 chemical reaction Methods 0.000 claims description 4
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
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- 239000007787 solid Substances 0.000 description 6
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- 125000003118 aryl group Chemical group 0.000 description 5
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
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- 238000005259 measurement Methods 0.000 description 4
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- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
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- 239000005056 polyisocyanate Substances 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical class NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- MLKGHQNOKUCQBA-UHFFFAOYSA-N (2-methyl-4-phenylphenyl)-phenylmethanone Chemical compound CC1=CC(C=2C=CC=CC=2)=CC=C1C(=O)C1=CC=CC=C1 MLKGHQNOKUCQBA-UHFFFAOYSA-N 0.000 description 1
- ITKPCHYKBRFJPV-UHFFFAOYSA-N (2-phenylphenyl) prop-2-eneperoxoate Chemical compound C=CC(=O)OOC1=CC=CC=C1C1=CC=CC=C1 ITKPCHYKBRFJPV-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
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- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
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- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- G—PHYSICS
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
Description
本発明は、メディア式湿式分散機を用いた無機微粒子分散液の製造方法、本製造方法により得られる無機微粒子分散液を含む硬化性組成物、及び該硬化性組成物を硬化して得られる光学部材用の硬化物に関する。 The present invention relates to a method for producing an inorganic fine particle dispersion using a media-type wet disperser, a curable composition containing the inorganic fine particle dispersion obtained by this production method, and an optical material obtained by curing the curable composition. The present invention relates to a cured product for members.
光学部材用の硬化物、例えば輝度向上用プリズムシートの場合、硬化樹脂層を高屈折率化することによってバックライトの正面輝度を向上させることができ、また、例えばフレネルレンズの場合、樹脂層を高屈折率とする程レンズパターンを浅くすることが可能なので、金型からの離型が容易となることにより生産性が向上できる等の由から、樹脂硬化物の高屈折率化が望まれている。 In the case of a cured product for an optical member, for example, a prism sheet for improving brightness, the front brightness of the backlight can be improved by increasing the refractive index of the cured resin layer. Since the lens pattern can be made shallower as the refractive index becomes higher, it is desirable to increase the refractive index of the cured resin because the mold can be easily released from the mold and productivity can be improved. Yes.
このような光学部材用の硬化物、特に光学シートの製造方法としては、例えば、プレス法、切削法、押し出し法等を適用し、液晶向上用プリズムシート、プロジェクションテレビ用フレネルレンズ、レンチキュラーレンズ等を得る方法が提案されている（例えば、特許文献１参照。）。 As a method for producing such a cured product for an optical member, particularly an optical sheet, for example, a press method, a cutting method, an extrusion method, etc. are applied, and a prism sheet for improving liquid crystal, a Fresnel lens for projection television, a lenticular lens, etc. An obtaining method has been proposed (see, for example, Patent Document 1).
しかし、何れの製法も生産性が低いことから、現在は透明プラスチックシート等の透明シート状基材の上に活性エネルギー線硬化性組成物によりプリズム層、レンズ層等の光学樹脂層を形成する方法が利用されている。 However, since any production method has low productivity, a method of forming an optical resin layer such as a prism layer or a lens layer on a transparent sheet-like base material such as a transparent plastic sheet by an active energy ray curable composition at present. Is being used.
このような硬化性組成物に、高硬度および耐擦傷性を付与するために、シリカやジルコニア等の無機酸化物の粒子分散液の併用が記載されている（例えば、特許文献２参照）。 In order to impart high hardness and scratch resistance to such a curable composition, the combined use of particle dispersions of inorganic oxides such as silica and zirconia is described (for example, see Patent Document 2).
また、ジルコニア粒子分散液を得る方法としては、透明分散させるためにアセチルアセトン系分散助剤を用いて、０．０５ｍｍ以上のメディアで分散する方法が記載されている（例えば、特許文献３参照）。当該法によれば、分散粒径の小さなジルコニア粒子分散液を得ることができるという。しかし、アセチルアセトン系分散助剤を用いた場合には、熱や光による劣化・着色を起こしやすい欠点を有する。 Further, as a method for obtaining a zirconia particle dispersion, a method of dispersing with a medium of 0.05 mm or more using an acetylacetone-based dispersion aid for transparent dispersion is described (for example, see Patent Document 3). According to this method, a zirconia particle dispersion having a small dispersed particle diameter can be obtained. However, when an acetylacetone-based dispersion aid is used, there is a drawback that it is liable to cause deterioration or coloring due to heat or light.
メディア式湿式分散機に供給する各原料、即ち、酸化ジルコニウムナノ粒子、分散剤、分散媒、シランカップリング剤の中で、シランカップリング剤を最後に供給することを特徴とする無機微粒子分散液の製造方法についても提案されている（例えば、特許文献４参照。）。前記特許文献４の製造方法によれば、透明性が高く、熱に対しても安定で、耐黄変性にも優れる光学部材用硬化物の製造が可能となるという。しかし、この方法では、３０μｍ以下の小粒子径のメディアを使用し、且つ分散時の固形分濃度を低くするマイルドな分散条件にしないと過分散が起きるという問題がある。小さい粒子径のメディアは、非常に高価であると同時に使用できる分散機が限られる。また、小さい粒子径のメディアを使用したり、固形分濃度を低くしたりすると、分散効率が悪く、工程時間が著しく長くなってしまう。他に多量の分散剤を使用して分散する方法もあるが、得られる硬化組成物の屈折率が低くなるという問題点も内包する。 Inorganic fine particle dispersion characterized in that the silane coupling agent is supplied last among the raw materials to be supplied to the media-type wet disperser, ie, zirconium oxide nanoparticles, dispersant, dispersion medium, and silane coupling agent. The manufacturing method has also been proposed (see, for example, Patent Document 4). According to the production method of Patent Document 4, it is possible to produce a cured product for an optical member that is highly transparent, stable against heat, and excellent in yellowing resistance. However, this method has a problem in that overdispersion occurs unless a medium having a small particle diameter of 30 μm or less is used and the mild dispersion condition for lowering the solid content concentration during dispersion is used. Small particle size media is very expensive and at the same time limited dispersers. In addition, when a medium having a small particle diameter is used or the solid content concentration is lowered, the dispersion efficiency is poor and the process time is remarkably increased. Although there is another method of dispersing using a large amount of a dispersant, the problem that the refractive index of the resulting cured composition is lowered is also included.
分散機に供給する各原料、即ち、金属酸化物ナノ粒子の凝集体、分散剤、金属アルコキシド、溶媒を解砕する前に全て混合して分散する製造方法も提案されている（例えば、特許文献５参照）。前記特許文献５では、当該製法により、分散剤の量を減らすことが可能で、ブリードアウトや硬度低下といった問題を解決できると記載されているが、この方法では分散効率が悪く、工程時間が著しく長くなり、生産効率が低くなる問題がある。 There has also been proposed a production method in which each raw material to be supplied to a disperser, that is, agglomerates of metal oxide nanoparticles, a dispersant, a metal alkoxide, and a solvent are all mixed and dispersed before crushing (for example, Patent Documents). 5). In Patent Document 5, it is described that the amount of the dispersant can be reduced by the production method, and problems such as bleed out and hardness reduction can be solved. There is a problem that the production efficiency becomes low due to the lengthening.
本発明が解決しようとする課題は、上記背景技術に鑑み、少ない分散剤の量で安定な分散体を得ることで、高屈折率の光学部材用硬化物を得ることにある。 In view of the above background art, the problem to be solved by the present invention is to obtain a cured product for optical members having a high refractive index by obtaining a stable dispersion with a small amount of dispersant.
同時に、非常に高価であると同時に使用できる分散機も限られる小粒子径のメディアを使用せずに、固形分濃度が高い条件下で過分散することなく、分散工程時間を大幅に短縮することができる無機微粒子分散液の製造方法を提供することにある。 At the same time, the disperser that can be used at the same time is very expensive, without using a medium with a small particle size, and without significantly overdispersing under high solid content conditions, greatly reducing the dispersion process time It is an object of the present invention to provide a method for producing an inorganic fine particle dispersion.
本発明者らは、上記課題を解決するため鋭意検討を行った結果、メディア式湿式分散機を用い、酸化ジルコニウムナノ粒子を分散する際に、分散剤を最後に供給することで、上記課題を解決できることを見出した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have used the media-type wet disperser to supply the dispersant at the end when dispersing the zirconium oxide nanoparticles. I found that it can be solved.
即ち、本発明は、メディア式湿式分散機を用いた無機微粒子分散液の製造方法であって、下記（Ａ）〜（Ｄ）を湿式分散機に供給するに際し、少なくとも（Ｄ）を最後に供給することを特徴とする無機微粒子分散液の製造方法を提供するものである。
（Ａ）酸化ジルコニウムナノ粒子
（Ｂ）シランカップリング剤
（Ｃ）分散媒
（Ｄ）分散剤That is, the present invention is a method for producing an inorganic fine particle dispersion using a media-type wet disperser, and when supplying the following (A) to (D) to a wet disperser, at least (D) is supplied last. The present invention provides a method for producing an inorganic fine particle dispersion.
(A) Zirconium oxide nanoparticles (B) Silane coupling agent (C) Dispersion medium (D) Dispersant
更に、本発明は、当該製造方法により製造される無機微粒子分散液を含む硬化性組成物、及び該硬化性組成物を硬化して得られる光学部材用に好適な硬化物を提供するものである。 Furthermore, this invention provides the curable composition containing the inorganic fine particle dispersion liquid manufactured by the said manufacturing method, and the hardened | cured material suitable for optical members obtained by hardening | curing this curable composition. .
本発明によれば、上記特徴を有する製造方法を提供することにより、少ない分散剤の量であっても安定な分散体を得ることで、高屈折率の光学部材用硬化物を得ることができる。 According to the present invention, a cured product for an optical member having a high refractive index can be obtained by providing a stable dispersion even with a small amount of dispersant by providing a production method having the above characteristics. .
また、該製造方法は、非常に高価であると同時に使用できる分散機も限られる小粒子径のメディアを使用せずに、固形分濃度が高い条件下で過分散することなく、分散工程時間を大幅に短縮することが可能になる。 In addition, the production method is very expensive, and at the same time, the dispersion process time can be reduced without using a medium having a small particle diameter, which can be used in a limited amount, and without overdispersing under a high solid content condition. It can be greatly shortened.
以下、本発明を詳細に説明する。
本発明に用いられるメディア式湿式分散機は、通常公知のものを制限なく使用することができる。このような分散機としては、例えば、ビーズミル（アシザワファインテック株式会社製スターミルＬＭＺ−０１５、寿工業（株）製ウルトラアペックスミルＵＡＭ−０１５等）を挙げることができるが、本発明に使用されるメディア式湿式分散機はこれに限らない。Hereinafter, the present invention will be described in detail.
As the media type wet disperser used in the present invention, generally known ones can be used without limitation. Examples of such a disperser include a bead mill (Star Mill LMZ-015 manufactured by Ashizawa Finetech Co., Ltd., Ultra Apex Mill UAM-015 manufactured by Kotobuki Industries Co., Ltd.), and is used in the present invention. The media type wet disperser is not limited to this.
本発明に使用されるメディアは、通常公知のビーズであれば特に制限はないが、好ましくは、ジルコニア、アルミナ、シリカ、ガラス、炭化珪素、窒化珪素を例示できる。メディアの平均粒径としては、５０〜５００μｍが好ましく、１００〜２００μｍのメディアがより好ましい。粒子径が５０μｍ以上であれば、原料粉に対する衝撃力が適正であり、分散に過度な時間を要しない。一方、メディアの粒子径が５００μｍ以下であれば、原料粉に対する衝撃力が適正であることから、分散された粒子の表面エネルギーの増大を抑制でき、再凝集を防止できる。 The medium used in the present invention is not particularly limited as long as it is a generally known bead, but preferred examples include zirconia, alumina, silica, glass, silicon carbide, and silicon nitride. The average particle diameter of the media is preferably 50 to 500 μm, more preferably 100 to 200 μm. When the particle diameter is 50 μm or more, the impact force on the raw material powder is appropriate, and an excessive time is not required for dispersion. On the other hand, if the particle diameter of the media is 500 μm or less, the impact force against the raw material powder is appropriate, so that an increase in the surface energy of the dispersed particles can be suppressed and reaggregation can be prevented.
また、原料粉の粉砕初期に、衝撃力の大きい大粒径のメディアを使用し、分散された粒子の粒径が小さくなってから、再凝集のおきにくい小粒径のメディアを使用する２段階の方法により、分散工程時間を短くすることもできる。 Also, in the initial stage of pulverizing the raw material powder, a medium having a large particle size with a large impact force is used, and a medium having a small particle size that is difficult to re-aggregate after the particle size of the dispersed particles becomes small is used. By this method, the dispersion process time can be shortened.
また、メディアは、得られる分散液の光透過度の低下を抑制できる観点より、十分に研磨したものを使用することが望ましい。 Further, it is desirable to use a sufficiently polished media from the viewpoint of suppressing a decrease in light transmittance of the obtained dispersion.
本発明で使用する（Ａ）酸化ジルコニウムナノ粒子としては、通常公知のものを用いることができ、粒子の形状は、特に限定されるものではないが、例えば、球状、中空状、多孔質状、棒状、板状、繊維状、又は不定形であり、好ましくは球状である。また、一次粒径は、１〜５０ｎｍものが好ましく、特に１〜３０ｎｍのものが好ましい。結晶構造も特に限定されないが、単斜晶系が好ましい。 As the (A) zirconium oxide nanoparticles used in the present invention, generally known particles can be used, and the shape of the particles is not particularly limited, but for example, spherical, hollow, porous, It is rod-shaped, plate-shaped, fibrous, or amorphous, preferably spherical. The primary particle size is preferably 1 to 50 nm, particularly preferably 1 to 30 nm. The crystal structure is not particularly limited, but a monoclinic system is preferable.
本発明で使用する（Ｂ）シランカップリング剤としては、下記のものを挙げることができるが、これらに限らない。 Examples of the (B) silane coupling agent used in the present invention include, but are not limited to, the following.
（メタ）アクリロイルオキシ系のシランカップリング剤としては、３−（メタ）アクリロイルオキシプロピルトリメチルシラン、３−（メタ）アクリロイルオキシプロピルメチルジメトキシシラン、３−（メタ）アクリロイルオキシプロピルトリメトキシシラン、３−（メタ）アクリロイルオキシプロピルメチルジエトキシシラン、３−（メタ）アクリロイルオキシプロピルトリエトキシシランが例示される。アクリロキシ系のシランカップリング剤としては、３−アクリロキシプロピルトリメトキシシランが例示される。 Examples of the (meth) acryloyloxy-based silane coupling agent include 3- (meth) acryloyloxypropyltrimethylsilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3 -(Meth) acryloyloxypropylmethyldiethoxysilane and 3- (meth) acryloyloxypropyltriethoxysilane are exemplified. Examples of the acryloxy silane coupling agent include 3-acryloxypropyltrimethoxysilane.
ビニル系のシランカップリング剤としては、アリルトリクロロシラン、アリルトリエトキシシラン、アリルトリメトキシシラン、ジエトキシメチルビニルシラン、トリクロロビニルシラン、ビニルトリクロルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シランが例示される。 Examples of vinyl silane coupling agents include allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2- Illustrative is methoxyethoxy) silane.
エポキシ系のシランカップリング剤としては、ジエトキシ（グリシディルオキシプロピル）メチルシラン、２−（３、４エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−ブリシドキシプロピルトリエトキシシランが例示される。スチレン系のシランカップリング剤としては、ｐ−スチリルトリメトキシシランが例示される。 Epoxy-based silane coupling agents include diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyl. Examples include diethoxysilane and 3-bridoxypropyl triethoxysilane. Examples of the styrene-based silane coupling agent include p-styryltrimethoxysilane.
アミノ系のシランカップリング剤としては、Ｎ−２（アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−トリエトキシシリル−Ｎ−（１、３−ジメチル−ブチリデン）プロピルアミン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランが例示される。 As amino-based silane coupling agents, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-amino Propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltri An example is methoxysilane.
ウレイド系のシランカップリング剤としては、３−ウレイドプロピルトリエトキシシランが例示される。クロロプロピル系のシランカップリング剤としては、３−クロロプロピルトリメトキシシランが例示される。メルカプト系のシランカップリング剤としては、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキンシランが例示される。スルフィド系のシランカップリング剤としては、ビス（トリエトキシシリルプロピル）テトラスルファイドが例示される。イソシアネート系のシランカップリング剤としては、３−イソシアネートプロピルトリエトキシシランが例示される。アルミニウム系カップリング剤としては、アセトアルコキシアルミニウムジイソプロピレートが例示される。 Examples of the ureido silane coupling agent include 3-ureidopropyltriethoxysilane. Examples of the chloropropyl-based silane coupling agent include 3-chloropropyltrimethoxysilane. Examples of mercapto-based silane coupling agents include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethinesilane. Examples of the sulfide-based silane coupling agent include bis (triethoxysilylpropyl) tetrasulfide. Examples of the isocyanate-based silane coupling agent include 3-isocyanatopropyltriethoxysilane. Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.
このようなシランカップリング剤の中でも、（メタ）アクリロイルオキシ基、グリシジル基、エポキシシクロヘキシル基を有するものが好ましく、特に３−（メタ）アクリロイルオキシプロピルトリメトキシシランが最も好ましい。 Among such silane coupling agents, those having a (meth) acryloyloxy group, a glycidyl group, and an epoxycyclohexyl group are preferable, and 3- (meth) acryloyloxypropyltrimethoxysilane is most preferable.
本発明で用いる（Ｃ）分散媒は、前記（Ａ）酸化ジルコニウムナノ粒子を分散させるものであれば特に制限はないが、２５℃における粘度が２００ｍＰａ・ｓ以下の有機溶剤、（メタ）アクリルモノマー、又は（メタ）アクリレートオリゴマーを単独で、あるいは、これらを組み合わせて用いることが好ましい。 The (C) dispersion medium used in the present invention is not particularly limited as long as it can disperse the (A) zirconium oxide nanoparticles, but an organic solvent having a viscosity at 25 ° C. of 200 mPa · s or less, a (meth) acrylic monomer. Or (meth) acrylate oligomers are preferably used alone or in combination.
２５℃における粘度が２００ｍＰａ・ｓ以下であれば、分散時の粘度が適正であることにより、分散機におけるメディアを分離することが容易となる。なお、本発明における粘度の測定は、通常公知の方法により測定でき、用いられる測定器としては、Ｂ型粘度計を挙げることができる。 When the viscosity at 25 ° C. is 200 mPa · s or less, it is easy to separate the media in the disperser because the viscosity at the time of dispersion is appropriate. In addition, the measurement of the viscosity in this invention can be normally measured by a well-known method, and a B-type viscosity meter can be mentioned as a measuring device used.
前記有機溶剤としては、好ましくは、例えばエタノール、イソプロパノール、ブタノール、シクロヘキサノール、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、酢酸エチル、酢酸プロピル、酢酸ブチル、メチルセロソルブ、セロソルブ、ブチルセロソルブ、セロソルブアセテート、テトラヒドロフラン、１，４−ジオキサン、ｎ−ヘキサン、シクロペンタン、トルエン、キシレン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、ジクロロメタン、トリクロロエタン、トリクロロエチレン、ハイドロフルオロエーテル等を挙げることができる。 The organic solvent is preferably ethanol, isopropanol, butanol, cyclohexanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, methyl cellosolve, cellosolve, butyl cellosolve, cellosolve acetate, tetrahydrofuran, 1, Examples include 4-dioxane, n-hexane, cyclopentane, toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, dichloromethane, trichloroethane, trichloroethylene, hydrofluoroether, and the like.
前記（メタ）アクリルモノマーとしては、特に、フェノキシエチルアクリレート、フェノキシ２−メチルエチルアクリレート、フェノキシエトキシエチルアクリレート、３−フェノキシ−２−ヒドロキシプロピルアクリレート、２−フェニルフェノキシエチルアクリレート、ベンジルアクリレート、フェニルアクリレート、フェニルベンジルアクリレート、パラクミルフェノキシエチルアクリレート等の、芳香環含有アクリレートは屈折率が高く、好ましく用いることができる。 Examples of the (meth) acrylic monomer include phenoxyethyl acrylate, phenoxy 2-methylethyl acrylate, phenoxyethoxyethyl acrylate, 3-phenoxy-2-hydroxypropyl acrylate, 2-phenylphenoxyethyl acrylate, benzyl acrylate, phenyl acrylate, Aromatic ring-containing acrylates such as phenylbenzyl acrylate and paracumylphenoxyethyl acrylate have a high refractive index and can be preferably used.
また、２−アクリロイロキシエチルヘキサヒドロフタレート、シクロヘキシルアクリレート、ジシクロペンタニルアクリレート、テトラヒドロフルフリルアクリレート、ジシクロペンタニルメタクリレート、イソボニルメタクリレート等の脂環骨格含有アクリレートはアッベ数が高く、光学材料として好ましく用いることができる。 In addition, alicyclic skeleton-containing acrylates such as 2-acryloyloxyethyl hexahydrophthalate, cyclohexyl acrylate, dicyclopentanyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentanyl methacrylate, and isobornyl methacrylate have a high Abbe number and are optical materials. Can be preferably used.
また、メチル（メタ）アクリレート、オクチル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、エチレンオキシド変性アルキル（メタ）アクリレート、プロピレンオキシド変性アルキル（メタ）アクリレート、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレートなどの単官能アルキル（メタ）アクリレートは低粘度であり、好ましく用いることができる。 Also, methyl (meth) acrylate, octyl (meth) acrylate, isostearyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylene oxide modified alkyl (meth) acrylate, propylene oxide modified alkyl (meth) Monofunctional alkyl (meth) acrylates such as acrylate, hydroxyethyl (meth) acrylate, and hydroxypropyl (meth) acrylate have a low viscosity and can be preferably used.
また、（ポリ）エチレングリコールジ（メタ）アクリレート、（ポリ）プロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート等の２官能（メタ）アクリレートや、グリセロールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、リン酸トリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート等の３，４官能（メタ）アクリレートおよびそれらのエチレンオキサイド、プロピレンオキサイド変性品は硬化物の高度を向上することができ、好ましく用いられる。 (Poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonane 3 such as bifunctional (meth) acrylate such as diol di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri (meth) acrylate phosphate, pentaerythritol tetra (meth) acrylate, etc. , Tetrafunctional (meth) acrylates and their ethylene oxide and propylene oxide modified products can improve the height of the cured product and are preferably used.
これらの（メタ）アクリルモノマーは、液状であって粘度が２００ｍＰａ・ｓ以上のものや室温において固体の（メタ）アクリルモノマーであっても、液状低粘度の（メタ）アクリルモノマーあるいは有機溶剤で希釈した混合物として、粘度を２００ｍＰａ・ｓ以下に低減して使用することも可能である。 Even if these (meth) acrylic monomers are liquid and have a viscosity of 200 mPa · s or higher, or solid (meth) acrylic monomers at room temperature, they are diluted with liquid (viscosity) (meth) acrylic monomers or organic solvents. It is also possible to use the mixture by reducing the viscosity to 200 mPa · s or less.
また、本発明の（Ｃ）分散媒として、エポキシ系モノマーも使用することができる。特に、ブチルグリシジルエーテル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテルなどのエポキシ化合物や、３，４−エポキシシクロヘキセニルメチル−３’，４’−エポキシシクロヘキセンカルボキシレート、１，２−エポキシ−４−ビニルシクロヘキサン、１，２：８，９ジエポキシリモネン、３，４−エポキシシクロヘキシルメチルメタアクリレートなどのシクロヘキセンオキシド化合物は好ましく用いることができる。 Moreover, an epoxy-type monomer can also be used as (C) dispersion medium of this invention. In particular, epoxy compounds such as butyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and 3,4-epoxycyclohexenylmethyl-3 ′, 4 Cyclohexene oxide compounds such as' -epoxycyclohexene carboxylate, 1,2-epoxy-4-vinylcyclohexane, 1,2: 8,9 diepoxy limonene, and 3,4-epoxycyclohexylmethyl methacrylate can be preferably used.
前記（メタ）アクリレートオリゴマーとしては、例えば、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレートがあげられる。 Examples of the (meth) acrylate oligomer include epoxy (meth) acrylate and urethane (meth) acrylate.
エポキシ（メタ）アクリレートとしては、例えば、分子構造中に芳香環骨格及びエポキシ基を有する化合物に、（メタ）アクリロイル基及びカルボキシル基を有する単量体を付加反応させて得られるエポキシ（メタ）アクリレートが挙げられる。分子構造中に芳香環骨格を有することで屈折率の高い化合物となる。 As an epoxy (meth) acrylate, for example, an epoxy (meth) acrylate obtained by adding a monomer having a (meth) acryloyl group and a carboxyl group to a compound having an aromatic ring skeleton and an epoxy group in the molecular structure. Is mentioned. By having an aromatic ring skeleton in the molecular structure, the compound has a high refractive index.
ウレタン（メタ）アクリレートとしては、例えば、ポリイソシアネート化合物と、分子構造中に水酸基を一つ有する（メタ）アクリレート化合物とを反応させて得られるウレタン（メタ）アクリレートや、ポリイソシアネート化合物と、分子構造中に水酸基を一つ有する（メタ）アクリレート化合物と、ポリオール化合物とを反応させて得られるウレタン（メタ）アクリレートが挙げられる。 Examples of the urethane (meth) acrylate include a urethane (meth) acrylate obtained by reacting a polyisocyanate compound with a (meth) acrylate compound having one hydroxyl group in the molecular structure, a polyisocyanate compound, and a molecular structure. Examples thereof include urethane (meth) acrylate obtained by reacting a (meth) acrylate compound having one hydroxyl group therein and a polyol compound.
前記ウレタン（メタ）アクリレートは、分子構造中に芳香環骨格を導入することで、屈折率の高い化合物となる。前記ポリイソシアネート化合物及び前記分子構造中に水酸基を一つ有する（メタ）アクリレート化合物のどちらか一方又は両方に、分子構造中に芳香環骨格を有するものを用いて得ることができる。 The urethane (meth) acrylate is a compound having a high refractive index by introducing an aromatic ring skeleton into the molecular structure. Either or both of the polyisocyanate compound and the (meth) acrylate compound having one hydroxyl group in the molecular structure can be obtained by using those having an aromatic ring skeleton in the molecular structure.
これらの（メタ）アクリレートオリゴマーは、液状であって粘度が２００ｍＰａ・ｓ以上のものや室温において固体の（メタ）アクリレートオリゴマーであっても、液状低粘度の（メタ）アクリルモノマーあるいは有機溶剤で希釈した混合物として、粘度を２００ｍＰａ・ｓ以下に低減して使用することも可能である。 Even if these (meth) acrylate oligomers are liquid and have a viscosity of 200 mPa · s or more, or solid (meth) acrylate oligomers at room temperature, they are diluted with liquid (viscosity) (meth) acrylic monomers or organic solvents. It is also possible to use the mixture by reducing the viscosity to 200 mPa · s or less.
本発明では、無機微粒子分散液の製造工程においては、（Ａ）酸化ジルコニウムナノ粒子、（Ｂ）シランカップリング剤、（Ｃ）分散媒を順次混合し、或いは一括で混合して得られた混合物に（Ｄ）分散剤を供給することに特徴を有する。前記（Ａ）〜（Ｃ）を分散機に供給する順番は特に限定はない。 In the present invention, in the production process of the inorganic fine particle dispersion, (A) zirconium oxide nanoparticles, (B) a silane coupling agent, and (C) a mixture obtained by sequentially mixing or collectively mixing. (D) It is characterized by supplying a dispersing agent. The order in which (A) to (C) are supplied to the disperser is not particularly limited.
前記（Ｄ）分散剤は、（Ａ）酸化ジルコニウムナノ粒子と親和性を有する基を含む化合物であれば、特に限定されないが、好ましい分散剤としては、カルボン酸、硫酸、スルホン酸或いはリン酸、又はそれらの塩等の酸基を有するアニオン系の分散剤を挙げることができる。これらの中でも好ましくは、リン酸エステル系分散剤である。前記（Ｄ）分散剤の使用量に関しては、特に限定されるものではないが、（Ａ）酸化ジルコニウムナノ粒子に対して、０．１〜３０質量％、好ましくは０．５〜１５質量％であり、従来必要とされている分散剤の使用量よりも少ない量であっても、安定性が良好な分散液を得ることができる。 The (D) dispersant is not particularly limited as long as it is a compound containing a group having affinity with (A) zirconium oxide nanoparticles, but preferred dispersants include carboxylic acid, sulfuric acid, sulfonic acid or phosphoric acid, Or the anionic dispersing agent which has acid groups, such as those salts, can be mentioned. Among these, a phosphate ester dispersant is preferable. Although it does not specifically limit regarding the usage-amount of the said (D) dispersing agent, It is 0.1-30 mass% with respect to (A) zirconium oxide nanoparticle, Preferably it is 0.5-15 mass%. In addition, a dispersion having good stability can be obtained even if the amount is smaller than the amount of dispersant used conventionally.
また得られる分散液において、前記（Ａ）酸化ジルコニウムナノ粒子と前記（Ｄ）分散剤の合計質量の割合が、２０質量％以上であることが、後述する硬化性組成物を調製する際に取り扱いが良好であると共に、分散工程時間の短縮が可能な上、分散液の安定性にも優れる点から好ましく、特に２５質量％〜３５質量％の範囲になるように調整することが好ましい。 Moreover, in the obtained dispersion liquid, the ratio of the total mass of the (A) zirconium oxide nanoparticles and the (D) dispersant is 20% by mass or more. Is preferable in that the dispersion process time can be shortened and the stability of the dispersion liquid is excellent, and it is particularly preferable to adjust to a range of 25 mass% to 35 mass%.
本発明の硬化性組成物は、前述の本発明の製造方法により得られる無機微粒子分散液を含むことを特徴とするものである。 The curable composition of the present invention comprises an inorganic fine particle dispersion obtained by the production method of the present invention described above.
本発明の硬化性組成物としては、本発明により得られる無機微粒子分散液を含み、更に、反応性基を有しても良い樹脂、フィラー、溶剤、光重合開始剤、増感剤、重合開始剤、エポキシ硬化剤および硬化促進剤、レベリング剤、密着助剤、離型剤、滑剤、紫外線吸収剤、酸化防止剤、熱安定剤等を含んでいてもよい The curable composition of the present invention contains a resin, a filler, a solvent, a photopolymerization initiator, a sensitizer, and a polymerization start which may contain the inorganic fine particle dispersion obtained by the present invention and may further have a reactive group. Agents, epoxy curing agents and curing accelerators, leveling agents, adhesion aids, mold release agents, lubricants, UV absorbers, antioxidants, heat stabilizers, etc.
本発明の硬化性組成物は、熱又は活性エネルギー線にて硬化させることができる。前記活性エネルギー線は、本発明の硬化性組成物が硬化を起こす活性エネルギー線であれば特に制限なく用いることができるが、特に紫外線を用いることが好ましい。 The curable composition of the present invention can be cured by heat or active energy rays. The active energy ray can be used without particular limitation as long as it is an active energy ray that causes the curable composition of the present invention to cure, but it is particularly preferable to use ultraviolet rays.
紫外線の発生源としては、蛍光ケミカルランプ、ブラックライト、低圧、高圧、超高圧水銀ランプ、メタルハライドランプ、太陽光線などがある。紫外線の照射強度は、終始一定の強度でも行って良いし、硬化途中で強度を変化させることにより、硬化後の物性を微調整することもできる。 Sources of ultraviolet rays include fluorescent chemical lamps, black lights, low pressure, high pressure, ultrahigh pressure mercury lamps, metal halide lamps, and solar rays. The irradiation intensity of the ultraviolet rays may be constant from beginning to end, or the physical properties after curing can be finely adjusted by changing the intensity during the curing.
紫外線の他、活性エネルギー線として、例えば可視光線、電子線類の活性エネルギー線も用いることができる。本発明の硬化性組成物は、２００〜４００ｎｍに固有の分光感度を有しており、光重合開始剤不在下に、通常用いられるエネルギー線の有するエネルギー、例えば、２０ｍＷ／ｃｍ２のエネルギー数値を挙げることができるが、これに限られない。In addition to ultraviolet rays, active energy rays such as visible light and electron beams can also be used as active energy rays. The curable composition of the present invention has an intrinsic spectral sensitivity in the range of 200 to 400 nm. In the absence of a photopolymerization initiator, the energy of a normally used energy beam, for example, an energy value of 20 mW / cm 2 is obtained. It can be mentioned, but is not limited to this.
本発明の硬化性組成物は、光重合開始剤不存在下に、紫外線又は可視光線の照射により硬化するが、硬化反応をより効率的に行なうために、種々の光重合開始剤を添加して硬化させることもできる。光重合開始剤としては、分子内結合開裂型と分子内水素引き抜き型の２種に大別できる。 The curable composition of the present invention is cured by irradiation with ultraviolet rays or visible light in the absence of a photopolymerization initiator, but various photopolymerization initiators are added to perform the curing reaction more efficiently. It can also be cured. Photopolymerization initiators can be broadly classified into two types: intramolecular bond cleavage type and intramolecular hydrogen abstraction type.
前記分子内結合開裂型の光重合開始剤としては、例えば、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、１−ヒドロキシシクロヘキシル−フェニルケトン、２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノンの如きアセトフェノン系；ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテルの如きベンゾイン類；２，４，６−トリメチルベンゾインジフェニルホスフィンオキシドの如きアシルホスフィンオキシド系；ベンジル、メチルフェニルグリオキシエステル、などが挙げられる。 Examples of the intramolecular bond cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl)- 2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino ( Acetophenones such as 4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphe Such acylphosphine oxide Le phosphine oxide; benzyl, methylphenyl glyoxy esters, and the like.
一方、分子内水素引き抜き型の光重合開始剤としては、例えば、ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル−４−フェニルベンゾフェノン、４，４′−ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４−ベンゾイル−４′−メチル−ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３′，４，４′−テトラ（ｔ−ブチルペルオキシカルボニル）ベンゾフェノン、３，３′−ジメチル−４−メトキシベンゾフェノンの如きベンゾフェノン系；２−イソプロピルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２，４−ジクロロチオキサントンの如きチオキサントン系；ミヒラ−ケトン、４，４′−ジエチルアミノベンゾフェノンの如きアミノベンゾフェノン系；１０−ブチル−２−クロロアクリドン、２−エチルアンスラキノン、９，１０−フェナンスレンキノン、カンファーキノン、などが挙げられる。 On the other hand, as an intramolecular hydrogen abstraction type photopolymerization initiator, for example, benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl Benzophenones such as diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2 Thioxanthone series such as 1,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; amino benzophenone series such as Michler-ketone, 4,4'-diethylaminobenzophenone; 10-butyl- - chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.
これらの光重合開始剤を使用する場合の配合量は、硬化性組成物の０．０１〜１０質量％の範囲が好ましい。 The blending amount when these photopolymerization initiators are used is preferably in the range of 0.01 to 10% by mass of the curable composition.
また、本発明の硬化性組成物は、硬化反応をより効率的に行なうために、光増感剤を併用することもできる。そのような光増感剤としては、例えば、トリエタノールアミン、メチルジエタノールアミン、トリイソプロパノールアミン、４−ジメチルアミノ安息香酸メチル、４−ジメチルアミノ安息香酸エチル、４−ジメチルアミノ安息香酸イソアミル、安息香酸（２−ジメチルアミノ）エチル、４−ジメチルアミノ安息香酸（ｎ−ブトキシ）エチル、４−ジメチルアミノ安息香酸２−エチルヘキシルの如きアミン類が挙げられる。 In addition, the curable composition of the present invention can be used in combination with a photosensitizer in order to perform the curing reaction more efficiently. Examples of such a photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid ( Examples include amines such as 2-dimethylamino) ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, and 2-dimethylhexyl 4-dimethylaminobenzoate.
光増感剤を使用する場合の配合量は、硬化性組成物中、０．０１〜１０質量％の範囲が好ましい。さらに、本発明の硬化性組成物には、用途に応じて、非反応性化合物、無機充填剤、有機充填剤、カップリング剤、粘着付与剤、消泡剤、レベリング剤、可塑剤、酸化防止剤、紫外線吸収剤、難燃剤、顔料、染料などを適宜併用することもできる。 The blending amount when using the photosensitizer is preferably in the range of 0.01 to 10% by mass in the curable composition. Furthermore, the curable composition of the present invention includes a non-reactive compound, an inorganic filler, an organic filler, a coupling agent, a tackifier, an antifoaming agent, a leveling agent, a plasticizer, and an antioxidant depending on the application. An agent, an ultraviolet absorber, a flame retardant, a pigment, a dye, and the like can be appropriately used in combination.
本発明で得られる硬化物は、光学用部材として、例えば、プラスチックレンズ、輝度向上フィルム（プリズムシート）、フィルム型液晶素子、タッチパネル、プラスチック光学部品等の反射防止膜等に好ましく用いることができる。 The cured product obtained in the present invention can be preferably used as an optical member, for example, as an antireflection film for a plastic lens, a brightness enhancement film (prism sheet), a film-type liquid crystal element, a touch panel, a plastic optical component, or the like.
以下に、実施例および比較例をもって本発明をより詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１
酸化ジルコニウムナノ粒子の粉体（商品名：ＵＥＰ−１００、第一稀元素化学工業株式会社製、一次粒子径１１ｎｍ）１６６．５ｇ、３−（メタ）アクリロイルオキシプロピルトリメトキシシラン（商品名：ＫＢＭ−５０３、信越化学工業株式会社製）２５．０ｇ、メチルエチルケトン（以下、ＭＥＫ）４１５．５ｇを混合し、分散攪拌機で３０分間攪拌し、粗分散を行った。得られた混合液を、メディア式湿式分散機であるアシザワファインテック株式会社製スターミルＬＭＺ−０１５で粒子径１００μｍのジルコニアビーズを用いて分散処理した。途中の粒子径を確認しながら、滞留時間１００分の分散処理を行った後、分散剤（商品名：ＤＩＳＰＥＲＢＹＫ−１１１、ビックケミー社製、燐酸エステル系）１７．５ｇを添加混合して、更に２０分間の分散処理により実施例１の分散液を得た。尚、分散剤を添加していない途中のサンプルの粒子径測定は、規定量の分散剤を添加し、攪拌した後に行った。Example 1
Zirconium oxide nanoparticle powder (trade name: UEP-100, manufactured by Daiichi Rare Element Chemical Co., Ltd., primary particle diameter 11 nm) 166.5 g, 3- (meth) acryloyloxypropyltrimethoxysilane (trade name: KBM) -503, manufactured by Shin-Etsu Chemical Co., Ltd.) 25.0 g and methyl ethyl ketone (hereinafter referred to as MEK) 415.5 g were mixed and stirred with a dispersion stirrer for 30 minutes for coarse dispersion. The obtained mixed liquid was subjected to a dispersion treatment using zirconia beads having a particle diameter of 100 μm with a star mill LMZ-015 manufactured by Ashizawa Finetech Co., Ltd., which is a media type wet disperser. While confirming the particle diameter in the middle, the dispersion treatment was performed for 100 minutes, and then 17.5 g of a dispersant (trade name: DISPERBYK-111, manufactured by Big Chemie, phosphate ester) was added and mixed, and further 20 A dispersion of Example 1 was obtained by a dispersion treatment for minutes. In addition, the particle diameter measurement of the sample in the middle of not adding the dispersant was performed after adding a prescribed amount of the dispersant and stirring.
実施例２
実施例１の分散剤をディスパロンＰＷ−３６（楠本化成株式会社製、燐酸エステル系）１６．７ｇに変更した以外は実施例１と同じ条件で分散処理を行った。Example 2
Dispersion treatment was performed under the same conditions as in Example 1 except that the dispersant of Example 1 was changed to 16.7 g of Disparon PW-36 (manufactured by Enomoto Kasei Co., Ltd., phosphate ester type).
実施例３
実施例１のシランカップリング剤を３３．３g、分散剤を２６．２gに変更した以外は、実施例１と同じ条件で分散処理を行った。Example 3
The dispersion treatment was performed under the same conditions as in Example 1 except that the silane coupling agent in Example 1 was changed to 33.3 g and the dispersant was changed to 26.2 g.
比較例１
酸化ジルコニウムナノ粒子の粉体（商品名：ＵＥＰ−１００、第一稀元素化学工業株式会社製、一次粒子径１１ｎｍ）１６６．５ｇ、３−（メタ）アクリロイルオキシプロピルトリメトキシシラン（商品名：ＫＢＭ−５０３、信越化学工業株式会社製）２５．０ｇ、分散剤（商品名：ＤＩＳＰＥＲＢＹＫ−１１１、ビックケミー社製）１７．５ｇ、ＭＥＫ４１５．５ｇを混合し、分散攪拌機で３０分間攪拌し、粗分散を行った。得られた混合液を、メディア式湿式分散機であるアシザワファインテック株式会社製スターミルＬＭＺ−０１５で粒子径１００μｍのジルコニアビーズを用いて分散処理した。途中の粒子径を確認しながら分散処理を進めたが、処理２００分後の粒子径が増大し過分散となった。Comparative Example 1
Zirconium oxide nanoparticle powder (trade name: UEP-100, manufactured by Daiichi Rare Element Chemical Co., Ltd., primary particle diameter 11 nm) 166.5 g, 3- (meth) acryloyloxypropyltrimethoxysilane (trade name: KBM) -503, manufactured by Shin-Etsu Chemical Co., Ltd.) 25.0 g, dispersant (trade name: DISPERBYK-111, manufactured by Big Chemie) 17.5 g, MEK 415.5 g were mixed and stirred with a dispersion stirrer for 30 minutes to give coarse dispersion. went. The obtained mixed liquid was subjected to a dispersion treatment using zirconia beads having a particle diameter of 100 μm with a star mill LMZ-015 manufactured by Ashizawa Finetech Co., Ltd., which is a media type wet disperser. The dispersion process was advanced while confirming the particle diameter on the way, but the particle diameter increased 200 minutes after the treatment, resulting in overdispersion.
比較例２
比較例１のシランカップリング剤を３３．３g、分散剤を２６．２gに変更した以外は、比較例１と同じ条件で分散処理を行った。滞留時間４００分の分散処理により比較例２の分散液を得た。Comparative Example 2
The dispersion treatment was performed under the same conditions as in Comparative Example 1 except that the silane coupling agent of Comparative Example 1 was changed to 33.3 g and the dispersant was changed to 26.2 g. A dispersion of Comparative Example 2 was obtained by a dispersion treatment with a residence time of 400 minutes.
比較例３
酸化ジルコニウムナノ粒子の粉体（商品名：ＵＥＰ−１００、第一稀元素化学工業株式会社製、一次粒子径１１ｎｍ）１６６．５ｇ、分散剤（商品名：ＤＩＳＰＥＲＢＹＫ−１１１、ビックケミー社製）１７．５ｇ、ＭＥＫ４１５．５ｇを混合し、分散攪拌機で３０分間攪拌し、粗分散を行った。得られた混合液を、メディア式湿式分散機であるアシザワファインテック株式会社製スターミルＬＭＺ−０１５で粒子径１００μｍのジルコニアビーズを用いて分散処理した。分散処理開始直後から６０分にかけて、３−メタクロキシプロピルトリメトキシシラン（商品名：ＫＢＭ−５０３、信越化学工業株式会社製）２５．０ｇを一定速度で添加混合して、分散処理を続けた。途中の粒子径を確認しながら分散処理を進めたが、処理２５０分後の粒子径が増大し過分散となった。Comparative Example 3
16. Powder of zirconium oxide nanoparticles (trade name: UEP-100, manufactured by Daiichi Rare Element Chemical Co., Ltd., primary particle diameter 11 nm) 166.5 g, dispersant (trade name: DISPERBYK-111, manufactured by BYK Chemie) 5 g and 415.5 g of MEK were mixed and stirred with a dispersion stirrer for 30 minutes to perform coarse dispersion. The obtained mixed liquid was subjected to a dispersion treatment using zirconia beads having a particle diameter of 100 μm with a star mill LMZ-015 manufactured by Ashizawa Finetech Co., Ltd., which is a media type wet disperser. Over 60 minutes immediately after the start of the dispersion treatment, 25.0 g of 3-methacryloxypropyltrimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and mixed at a constant rate, and the dispersion treatment was continued. The dispersion treatment was advanced while confirming the particle diameter in the middle, but the particle diameter increased 250 minutes after the treatment, resulting in overdispersion.
測定例＜分散液中の酸化ジルコニウムナノ粒子の分散粒径測定＞
作製１日後（２５℃保管）の分散液中の酸化ジルコニウムナノ粒子の分散粒径を、大塚電子株式会社製の粒度分布測定装置ＥＬＳＺ−１０００を用いて２５℃で測定した。分散液と同等の分散媒で酸化ジルコニウム濃度０．１質量％に希釈して、メジアン径を体積基準で測定した。Measurement example <Measurement of dispersed particle size of zirconium oxide nanoparticles in dispersion>
One day after the production (stored at 25 ° C.), the dispersed particle size of the zirconium oxide nanoparticles in the dispersion was measured at 25 ° C. using a particle size distribution measuring device ELSZ-1000 manufactured by Otsuka Electronics Co., Ltd. The median diameter was measured on a volume basis by diluting to a zirconium oxide concentration of 0.1% by mass with a dispersion medium equivalent to the dispersion.
注１）酸化ジルコニウムナノ粒子：ＵＥＰ−１００
注２）ディスパロンＰＷ−３６（商品名、楠本化成株式会社製）
注３）ＤＩＳＰＥＲＢＹＫ−１１１（商品名、ビックケミー社製）
注４）ＫＢＭ−５０３（商品名、信越化学工業株式会社製）Note 1) Zirconium oxide nanoparticles: UEP-100
Note 2) Disparon PW-36 (trade name, manufactured by Enomoto Kasei Co., Ltd.)
Note 3) DISPERBYK-111 (trade name, manufactured by Big Chemie)
Note 4) KBM-503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
実施例４：硬化性組成物（１）の調製
実施例１で作製した酸化ジルコニウムの分散液９３．７質量部にＵＶモノマーとして、フルオレンアクリレート（商品名：ＯＧＳＯＬ ＥＡ−０２００、大阪ガスケミカル株式会社製）４．７質量部、２−フェニルフェノキシアクリレート（商品名：Ｍ１１４２、Ｍｉｗｏｎ Ｓｐｅｃｉａｌｔｙ Ｃｈｅｍｉｃａｌ社製）２０．５質量部を加え、エバポレーターで揮発成分を減圧除去した。この得られた組成物に光重合開始剤として、２，４，６−トリメチルベンゾイルフェニルフォスフィンオキサイド（ＬＵＣＩＲＩＮ ＴＰＯ、ＢＡＳＦ社製）１．６質量部、１−ヒドロキシシクロヘキシル−フェニルケトン（商品名：イルガキュア１８４、ＢＡＳＦ社製）０．５質量部を添加して光硬化性組成物（１）を調製した。Example 4: Preparation of curable composition (1) Fluorene acrylate (trade name: OGSOL EA-0200, Osaka Gas Chemical Co., Ltd.) was used as a UV monomer in 93.7 parts by mass of the zirconium oxide dispersion prepared in Example 1. (Made by) 4.7 parts by mass, 2-phenylphenoxy acrylate (trade name: M1142, manufactured by Miwon Specialty Chemical) 20.5 parts by mass were added, and the volatile components were removed under reduced pressure with an evaporator. As a photopolymerization initiator, 1.6 parts by mass of 2,4,6-trimethylbenzoylphenylphosphine oxide (LUCIRIN TPO, manufactured by BASF), 1-hydroxycyclohexyl-phenylketone (trade name: Irgacure 184 (manufactured by BASF) 0.5 parts by mass was added to prepare a photocurable composition (1).
実施例５：硬化性組成物（２）の調製
実施例２で作製した酸化ジルコニウムの分散液９３．６質量部を用いて、実施例４と同様にして光硬化性組成物（２）を調製した。Example 5: Preparation of curable composition (2) Using 93.6 parts by mass of the zirconium oxide dispersion prepared in Example 2, a photocurable composition (2) was prepared in the same manner as in Example 4. did.
実施例６：硬化性組成物（３）の調製
実施例３で作製した酸化ジルコニウムの分散液９６．３質量部を用いて、実施例４と同様にして光硬化性組成物（３）を調製した。Example 6: Preparation of curable composition (3) A photocurable composition (3) was prepared in the same manner as in Example 4 using 96.3 parts by mass of the zirconium oxide dispersion prepared in Example 3. did.
比較例４：硬化性組成物（４）の調製
比較例２で作成した酸化ジルコニウムの分散液９６．３質量部を用いて、実施例４と同様にして光硬化性組成物（４）を調製した。Comparative Example 4: Preparation of Curable Composition (4) A photocurable composition (4) was prepared in the same manner as in Example 4 using 96.3 parts by mass of the zirconium oxide dispersion prepared in Comparative Example 2. did.
実施例７：硬化物（１）の作製
実施例４で得た光硬化性組成物（１）をガラス基板にアプリケーターで塗装し、空気中、１２０Ｗ／ｃｍ高圧水銀ランプにて１０００ｍＪ／ｃｍ２で光硬化して厚さ約１００μｍの硬化膜（１）を得た。Example 7: Preparation of cured product (1) The photocurable composition (1) obtained in Example 4 was coated on a glass substrate with an applicator, and was 1000 mJ / cm 2 in air using a 120 W / cm high-pressure mercury lamp. Photocured to obtain a cured film (1) having a thickness of about 100 μm.
実施例８〜９
実施例７と同様にして、実施例５、６において得られた光硬化性組成物（２）、（３）を用いて、それぞれ硬化膜（２）、（３）を得た。Examples 8-9
In the same manner as in Example 7, cured films (2) and (3) were obtained using the photocurable compositions (2) and (3) obtained in Examples 5 and 6, respectively.
比較例５
実施例７と同様にして、比較例４において得られた光硬化性組成物（４）を用いて、硬化膜（４）を得た。Comparative Example 5
In the same manner as in Example 7, a cured film (4) was obtained using the photocurable composition (4) obtained in Comparative Example 4.
硬化物の屈折率および透明性の測定方法
上記で得られた硬化物（硬化膜）について、アッベ屈折率計によって屈折率を、ヘーズメータで透明性を測定した。結果を、表２に示した。Method for Measuring Refractive Index and Transparency of Cured Product About the cured product (cured film) obtained above, the refractive index was measured with an Abbe refractometer, and the transparency was measured with a haze meter. The results are shown in Table 2.
本発明の製造方法により得られる無機微粒子分散液は、熱又は紫外線照射等により高屈折率を有する硬化物とすることができ、当該硬化物は光学用部材として好適に用いることができる。 The inorganic fine particle dispersion obtained by the production method of the present invention can be made into a cured product having a high refractive index by heat or ultraviolet irradiation, and the cured product can be suitably used as an optical member.
Claims (6)
（Ａ）酸化ジルコニウムナノ粒子
（Ｂ）（メタ）アクリロイルオキシ基、グリシジル基、エポキシシクロヘキシル基の何れかを有するシランカップリング剤
（Ｃ）有機溶剤、（メタ）アクリルモノマー、エポキシ系モノマー、及び（メタ）アクリレートオリゴマーからなる群から選ばれる１種以上の化合物である分散媒
（Ｄ）リン酸、カルボン酸、硫酸、或いはスルホン酸、又はそれらの塩である酸基を有するアニオン系の分散剤
工程１:前記（Ａ）〜（Ｃ）成分を含有する反応原料をメディア式湿式分散機に投入して分散させる工程
工程２：工程１の後、前記（Ｄ）成分を含有する反応原料をメディア式湿式分散機に投入して分散させる工程 A method for producing an inorganic fine particle dispersion using a media-type wet disperser, which comprises the following steps (A) to (D) as essential raw materials and comprising the following steps 1 and 2.
(A) Zirconium oxide nanoparticles (B) Silane coupling agent having any of (meth) acryloyloxy group, glycidyl group, and epoxycyclohexyl group (C) organic solvent, (meth) acryl monomer, epoxy monomer, and ( Dispersion medium (D) which is at least one compound selected from the group consisting of (meth) acrylate oligomers (D) Anionic dispersant process having an acid group which is phosphoric acid, carboxylic acid, sulfuric acid, sulfonic acid, or a salt thereof 1: The reaction raw material containing the components (A) to (C) is charged into a media type wet disperser and dispersed. Step 2: After step 1, the reaction raw material containing the component (D) is converted into a media type. The process of putting into a wet disperser and dispersing
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| KR20220078242A (en) * | 2020-12-03 | 2022-06-10 | 주식회사 케이씨텍 | Dispersion comprising metal oxide |
| KR20230029094A (en) * | 2021-08-23 | 2023-03-03 | 주식회사 케이씨텍 | Metal oxide dispersion, film composiotion for display and optical member for display |
| CN114573024A (en) * | 2022-03-18 | 2022-06-03 | 山东国瓷功能材料股份有限公司 | Zirconium oxide monomer type dispersion liquid, preparation method thereof, optical film and display screen |
| CN114605762B (en) * | 2022-04-21 | 2024-01-26 | 山东国瓷功能材料股份有限公司 | Nanometer zirconia dispersion liquid, preparation method and application |
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| TW201625480A (en) | 2016-07-16 |
| KR102353577B1 (en) | 2022-01-21 |
| TWI620710B (en) | 2018-04-11 |
| KR20170097602A (en) | 2017-08-28 |
| US20170342234A1 (en) | 2017-11-30 |
| CN107001067B (en) | 2019-09-20 |
| JPWO2016093014A1 (en) | 2017-04-27 |
| WO2016093014A1 (en) | 2016-06-16 |
| CN107001067A (en) | 2017-08-01 |
| US10253156B2 (en) | 2019-04-09 |
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